Manufacture of sulphur dyestuffs



Patented June 13, 1933 UNITED STATES PATENT: OFFICE HANS LEEMANN ANDWALTER WEHRLI, OFBASEL, SWITZERLAND, ASSIGNORS TO THE FIRM CHEMICALWORKS FORMER-LY SANDOZ, OF BASEL, SWITZERLAND MANUFACTURE or sULrHUR'nYEs'rUrrs No Drawing. Application filed June 2 6, 1930, Serial No.464,118, and in Great Britain July 6, 1929.

5 with alkali polysulphides.

known that from various It is already 7 azines, for instance fromhydroxylated azmes and their derivatives, safranines andtheirderivatives, iso-rosindulines etc. sulphurized,

13 violet-brown to red-brown dyestuffs can be obtained. It is also knownthat the color shades and the fastness properties of these dyestufis areimproved when the so-called melting process is carried out in presenceof 15 certain metals or metal salts, such as copper,

tion that far better results are obtained if, instead of the metals orcompounds above referred to as having already been used as addition tothe meltings, molybdenumormolybdenum compounds are employed. This wasnot to be foreseen, because until now molybdenum or molybdenum compoundsnever have been used in the manufacture of sulphurized dyestuffs. I 7

The new dyestuffs produced in the above described manner, that is whenthe melting process takes place in the presence ofmolybso much clearerand redder dyes when dyeing in a sodium sulphide bath in comparison withthe known sulphurized dyestuffs obtained by melting the same azines withthe addition of one of the metals above referred to or their salts. Forexample amino-hydroxytolazine which, when, melted in presence of copperor copper salts, yields redbrown sulphurized' dyestufls, when howeverbeing melted in presence of molybdenum or molybdenum compounds, yieldsbluish dark red dyestuffs. The action of molybdenum in this case isreally surprising and the possibility of producing, fromthe same primary7 material remarkably redder dyestuffs is of great practical value andconstitutes a real progress. A further advantage of the dyeings producedwith the new dyestuffs is their valuable property of being fast orstable in storing.

violet to violetsulphurized dyestuffs.

denum or molybdenum compounds give Various molybdenum compounds can beis not limitedto the compounds mentioned.

In the new process we may employ as azines those azines which, whenmelted in the already known manner, in presence or not of a metalliccompound, give from reddish-brown, reddish, bordeaux-red, reddish-Especially good results are obtained with hydroxylated azines and theiralkyl-, aryl-, halogenand like derivatives, or their carboxylic orsulphonio acids. nickel, cobalt, or their salts and compounds.

We have now made thesurprising observa The conditions of themeltingprocess (temperature, time, proportion of alkali polysulphide,quantity of the molybdenum compounds) may be modified within widelimits. The process can further be carried out in presence of the usualfusing or dissolving agents, as glycerine or alcohol, or under pressure.

The invention is illustrated by the following examples, the pjarts'beingby weight:

Example 1 86 parts of amino-hydrox'yph'enazine [I NH/ n are dissolved in80 parts of water and 171 parts of a 30% solution of caustic soda andallowed to run int-o a hot solution of sodiumpolysulphide prepared from173 parts of sulphur, 325 partsof crystallized sodium sulphide and 325parts of water. Thereupon,

28 parts of molybdic acid are added and the water is partiallyevaporated, until the boiling point has reached 110 C. Then the melt isheated for 3032 hours under a reflux condenser until the dyestufi' hasthe desired shade. The raw product can be used directly Example 2 58parts of amino-hydroxytolazine on3 N\ 5 p v a NHQ/ i N on are dissolvedin 60- parts of water and 38 parts of a 30% solution otcaustic sodaandallowed to run into a hot solution ofsodiumpolysulphide prepared bydissolving 180 parts of sulphur in 282 parts of sodium sulphide (60%)and 500 parts of water. After addition of 23 parts of ammoniummolybdate,

dissolved in .60 parts of water, the water is partially evaporated,until the boiling point has reached 120 T hen the melt is heated for1620 hours :under reflux until the dyestufi has thedesired shade. Theproduct dyes 20 cotton fibreiErom asodium sulphide bath dark red shades.

Ema mp le 1f the Example Qinsteadof'23 parts of ammonium :molybdate 24parts of phospho- 0 molyhdic acid are employed, the same dyeprepared bytreating the amine under pressure in an aqueous solution, is employed,aquite similardyestufi is obtained.

.Ewmmple If in the Example 2 instead of 58 parts ofamino-hydroxytolazine the same quantity of amino-hydroxytolazinecarboxylic acid 0133\UCOOH Nn/ N 1 on is employed, almost the samedyestuff is 0htained.

Example 6 If in the Example 2 instead of aminohydroxytolazine thecorresponding quantity of :dichloroamino-hydroxytolazineof the tor- CH3Z @131 NH/ ii on If in the Example 2 the amino-hydroxytolazine isreplaced by the same quantity of ethosafraninone a dyestufi results,which dyes the cotton fibre 7 from a sodium sulphide bathclearloluish-red shades.

What'we claim is: g :1. A process for the production of sulphurdyestuffs, which comprises heating .suchhydroxylated mines thatlbesidethe azine ring do not contain other heterocyclic rings, withsodium hydroxide and :sulphur in presence of substances containingmolybdenum.

2. process for the production .ofsulphur dyestuffs, which comprisesheating amino derivatives of such hydro-xylated azines, that .beside theazine ring do not contain other heterocyclic rings, with sodiumhydroxide I and sulphur in presence of substances containing molybdenum.V

3. A process for the production of sulphur dyestuffs, which comprisesheating :aminohydroxyphenazine with sodium hydroxide and sulphur inpresence of substances containing molybdenum.

4-,. A process "tor the production :of sulphur dyestuffs, whichcomprises heating amino- .hydroxyphenazine with a sodium polysulphide inpresence of molybdic acid.

.5. The sulphur dyestuffs deriving from hydroxylated azines which.beside the .azine ring do not contain other heterocyclic rings, andcontaining molybdenum, said dyestufis being in drystate generally darkpowders,

soluble in concentrated sulphuric acid with .a Yblue-vi-olet to redviolet coloration and which dye cellulose fibres from a sodium sulp-hidebath 'brownishered, red, reddish-violet to violet shades.

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